Microstructured Metal Electrodeposition at a Micellar Brush‐Decorated Interface

ABSTRACT Metal electrodeposition is usually interfered by stochastic ion arrival, local field amplification, and uncontrolled crystal growth, rendering it difficult to translate molecular‐level interfacial design into prescribed mesoscale architectures. Here, we report that surface‐emanated micellar brush with a forest‐like soft architecture can finely modulate the orientation and microstructure of metal electrodeposition. The poly( l ‐lactic acid)‐b‐poly(2‐vinylpyridine) micellar brush provides a hierarchically open nanoarray platform for continuous accumulation of metal ions through dynamical coordination with the pyridyl‐rich corona and sustained deposition of reduced metal at the inter‐micellar voids. Unlike conventional homopolymer coatings that mainly lead to flat deposition of Zn, such micellar‐brush layer promotes vertically aligned zinc blades through coupled ion funneling and oriented nanoconfinement. The resulting zinc anode reveals a low nucleation overpotential of ∼21 mV, a high Zn 2+ transference number of 0.79, a rapid rate of ∼24.2 µm h −1 at 10 mA cm −2 , and a polarization of only 18 mV upon reversible plating/stripping over 3000 h. The full cells integrated by vertically microstructured Zn anode with V 2 O 5 cathode retain 89.6% capacity after 1000 cycles at 1 A g −1 . This work establishes a general route to tailored metal microstructures through softly confined electrodeposition across a spatially directing and chemically associating polymer self‐assembly interfaces.